Although photochromic molecules have attracted widespread interest in various fields, solid-state photochromism remains a formidable challenge, owing to the substantial conformational constraints that hinder traditional molecular photoisomerization processes. Benefiting from the significant color change upon radical generation, chemical systems enabling a photoinduced radical (PIR) behavior through photoinduced electron transfer (PET) could be ideal candidates for solid-state photochromism within minimized need of conformational freedom. However, the transient nature of radicals causes a dilemma in this Scheme. Herein, we present a general crystal engineering strategy for rapidly generated (7-s irradiation to saturation) and ultra-stable (lasting 12 weeks) PIRs in the solid state, based on the anti-parallel alignment of para-hydroxyphenyl groups of persulfurated arenes to form a strong non-covalent network for efficient PET and radical stabilization. Using this strategy, a PIR platform was constructed, with a superior photochromic behavior remaining in different solid forms (even in the fully-ground sample) due to their transcendent crystallization ability. On this basis, our compounds can be further processed into reusable papers for light-writing, accompanied by water fumigation for modulating the reversible process. This work provides new insights into addressing solid-state photochromism and can inspire a wide range of optical material design from the switchable radical perspective.

Molecular emitters with multi-emissive properties are in high demand in numerous fields, while these properties basically depend on specific molecular conformation and packing. For amorphous systems, special molecular arrangement is unnecessary, but it remains challenging to achieve such luminescent behaviors. Herein, we present a general strategy that takes advantage of molecular rigidity and S 1 -T 1 energy gap balance for emitter design, which enables fluorescence–phosphorescence dual-emission properties in various solid forms, whether crystalline or amorphous. Subsequently, the amorphism of the emitters based polymethyl methacrylate films endowed an in situ regulation of the dual-emissive characteristics. With the ratiometric regulation of phosphorescence by external stimuli and stable fluorescence as internal reference, highly controllable luminescent color tuning (yellow to blue including white emission) was achieved. There properties together with a persistent luminous behavior is of benefit for an irreplaceable set of optical information combination, featuring an ultrahigh-security anti-counterfeiting ability. Our research introduces a concept of eliminating the crystal-form and molecular-conformational dependence of complex luminescent properties through emitter molecular design. This has profound implications for the development of functional materials.

Proton donating ability is known to be a key factor during most chemical, physical, and biological processes; therefore, quantifying such an ability visibly is crucial for further research. However, there has long been a lack of excellent models to fulfil such a quantitative visualization. Here, we designed and synthesized a series of fluorescent chemoprobes based on ortho-pyridinyl anilines, whose fluorescence signal showed a quantitative relationship with its intermolecular hydrogen bond strength. On this basis, the proton donating ability of the external proton donors through competitive hydrogen bond formation could be shown quantitatively by virtue of the changes of the fluorescence.

There are numerous ways to achieve light-induced self-assembly of gold nanoparticles, but most of them are through chemical reaction and slow. Ligands that can perform photoexcitation-induced aggregation were synthesized and modified onto gold nanoparticles. The leading functionalized nanoparticles exhibit highly efficient light-induced self-assembly properties and show high-contrast color fading in tens of seconds.

Polymer dots (PDs) have raised considerable research interest due to their advantages of designable nanostructures, high biocompatibility, versatile photoluminescent properties, and recyclability as nanophase. However, there remains a lack of in situ, real-time, and noncontact methods for synthesizing PDs. Here we report a rational strategy to synthesize PDs through a well-designed single-component precursor (an asymmetrical donor-acceptor-donor ' molecular structure) by photoirradiation at ambient temperature. In contrast to thermal processes that normally lack atomic economy, our method is mild and successive, based on an aggregation-promoted sulfonimidization triggered by photoinduced delocalized intrinsic radical cations for polymerization, followed by photooxidation for termination with structural shaping to form PDs. This synthetic approach excludes any external additives, rendering a conversion rate of the precursor exceeding 99%. The prepared PDs, as a single entity, can realize the integration of nanocore luminescence and precursor-transferred luminescence, showing 41.5% of the total absolute luminescence quantum efficiency, which is higher than most reported PD cases. Based on these photoluminescent properties, together with the superior biocompatibility, a unique membrane microenvironmental biodetection could be exemplified. This strategy with programming control of the single precursor can serve as a significant step toward polymer nanomanufacturing with remote control, high-efficiency, precision, and real-time operability.

Room-temperature phosphorescent carbon dots (RTPCDs) have attracted considerable interests due to their unique nanoluminescent characteristic with time resolution. However, it is still a formidable challenge to construct multiple stimuli-activated RTP behaviors on CDs. Since the address of this issue facilitates complex and high-regulatable phosphorescent applications, we here develop a novel strategy to achieve a multiple stimuli responsive phosphorescent activation on a single carbon-dot system (S-CDs), using persulfurated aromatic carboxylic acid as the precursor. The introduction of aromatic carbonyl groups and multiple S atoms can promote the intersystem crossing process to generate RTP characteristic of the produced CDs. Meanwhile, by introducing these functional surface groups into S-CDs, the RTP property can be activated by light, acid, and thermal stimuli in solution or in film state. In this way, multistimuli responsive and tunable RTP characteristics are realized in the single carbon-dot system. Based on this set of RTP properties, S-CDs is applied to photocontrolled imaging in living cells, anticounterfeit label, and multilevel information encryption. Our work will benefit the development of multifunctional nanomaterials together with extending their application scope.